JP2001075220A - Silver halide photographic emulsion and silver halide photographic sensitive material - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a silver halide photographic sensitive material high in sensitivity. SOLUTION: The silver halide photographic sensitive material has at least one silver halide emulsion layer on a support, and this silver halide emulsion contains silver halide grains having a spectral absorption maximum wavelength of <500 nm and a light absorptivity of >=60 or a spectral absorption maximum wavelength of >=500 nm and a light absorptivity of >=100, and at least one of sensitizing dyes to be used for spectrally sensitizing the silver halide grains has no charge in the molecule or has an intermolecular salt and the molecule has no charge as a whole and has one or more aromatic rings in the molecule and the silver halide photographic sensitive material is spectrally sensitized with these sensitizing dyes.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a spectrally sensitized silver halide photographic material.

[0002]

[Prior art]

Heretofore, great efforts have been made to increase the sensitivity of silver halide photographic materials. In a dye used for spectral sensitization of silver halide, the efficiency of transmitting light energy to silver halide is improved by increasing the light absorptivity, and a higher spectral sensitivity is achieved. Conceivable. However, the amount of sensitizing dye adsorbed on the surface of silver halide grains is limited, and ordinary sensitizing dyes are adsorbed in a monomolecular layer with almost fine packing, and a single layer completely covers the surface of silver halide grains. It is difficult to adsorb more dye chromophore than saturated adsorption (ie, one-layer adsorption). That is, even if the sensitizing dye is added in an amount equal to or more than the monolayer saturated adsorption amount, only the non-adsorbed (free) dye is increased. Therefore, at present, the absorptance of the incident light quantum of each silver halide grain in the spectral sensitization region is still low.

[0004] A method proposed to solve these points will be described below. PB Gilman, Jr., et al., Photographic Science and Engine Nearing (Photographic Science and and).
Engineering, Vol. 20, No. 3, No. 97 (1976), a cationic dye was adsorbed on the first layer, and an anionic dye was adsorbed on the second layer using electrostatic force. GB Bird et al., In U.S. Pat. No. 3,622,316, incorporated multiple dyes onto silver halide in multiple
sensitized by the contribution of the (ster) type excitation energy transfer.

Sugimoto et al., JP-A-63-138,341.
Nos. 64-84 and 244, spectral sensitization was performed by energy transfer from the luminescent dye. R. Steiger et al., Photographic Science and Engine Nearing (Photographic Science and)
Engineering, Vol. 27, No. 2, No. 59 (1983), an attempt was made to spectrally sensitize a gelatin-substituted cyanine dye by energy transfer. Conducted spectral sensitization by energy transfer from a cyclodextrin-substituted dye in JP-A-61-251842.

[0006] For so-called linked dyes which have two chromophores which are not separately conjugated but linked by a covalent bond, see, for example, US Pat. Nos. 2,393,351 and 2,42.
5,772, 2,518,732, 2,52
1,944, 2,592,196, European Patent 56
No. 5,083 and the like. However, these were not aimed at improving the light absorption rate. For the purpose of positively aiming at the improvement of the light absorption rate, GB Bird (A.B.
L. Borrr et al., In U.S. Pat. Nos. 3,622,317 and 3,976,493, incorporated a linked sensitizing dye molecule having a plurality of cyanine chromophores to increase light absorptivity and contribute to energy transfer. Sensitized. Ukai, Okazaki and Sugimoto disclose in JP-A-64-91134, at least one of a substantially non-adsorbing cyanine, merocyanine and hemicyanine dye containing at least two sulfo groups and / or carboxyl groups.
It has been proposed to couple to spectral sensitizing dyes that can be adsorbed on silver halide.

Further, L. C. Bishwakarma (L.
C. Vishwakarma) is disclosed in JP-A-6-57235.
In the above, a method of synthesizing a linked dye by a dehydration condensation reaction of two dyes was described. Further, Japanese Patent Application Laid-Open No. 6-27
No. 578 shows that a linked dye of monomethine cyanine and pentamethine oxonol has red sensitivity, but in this case, there is no overlap between oxonol emission and cyanine absorption, and a Forster type excitation energy between dyes. -Spectral sensitization due to migration does not occur, and high sensitivity cannot be expected due to the condensing action of the linked oxonol.

[0008] Also, R. L. Parton (RL
(Parton et al.) In EP 887,770 A1 proposed a linking dye having a specific linking group.

Also, M. Roberts (M.R.
Roberts et al. In US Pat. No. 4,950,587 proposed spectral sensitization with cyanine dye polymers.

As described above, many studies have been made to improve the light absorptivity, but none of them has a sufficient effect of increasing the sensitivity, and there is also a problem such as an increase in intrinsic desensitization and suppression of development. Was.

In particular, in the case of a color photographic material, it is necessary to keep the spectral sensitivity within a target wavelength range. Normally, in spectral sensitization of a silver halide light-sensitive material, the J band formed when adsorbed on the surface of silver halide grains is used instead of using the absorption of the sensitizing dye in a monomer state.
The J band has a sharp absorption shifted to a longer wavelength side than the monomer state, and thus is very useful for keeping light absorption and spectral sensitivity in a desired wavelength range. Therefore, even if the light absorption rate can be increased by multilayer adsorption of the sensitizing dye on the grain surface, when the second and subsequent dyes that do not directly adsorb to the silver halide grains are adsorbed in a monomer state. Causes a very wide absorption, which is not appropriate as the spectral sensitivity of the actual photosensitive material. On the other hand, each color gamut has a width of about 100 nm, and it is not preferable that an unnecessarily large sensitivity difference occurs for light in that range. From the above, the sensitizing dye is multilayer-adsorbed on the surface of the silver halide grains, and while increasing the light absorption area intensity per unit grain surface area, the absorption and spectral sensitivity are limited to the width of a desired color gamut, and There has been a demand for a technique for minimizing changes in spectral absorptance and sensitivity for light in that range. On the other hand, it was found that when the sensitizing dye was multi-layer adsorbed on the particle surface, the amount of gelatin adsorbed was reduced and the protective colloid ability was reduced, so that particle aggregation was likely to occur. Therefore, there has been a demand for a technique of adsorbing a sensitizing dye in a multilayer manner and suppressing particle aggregation.

We have made intensive studies to make the dye chromophore more adsorbed on silver halide grains,
For example, JP-A-10-239789 and JP-A-8-26900
No. 9, No. 10-123650 and Japanese Patent Application No. 7-75349, in which a dye having an aromatic group or a combination of a cationic dye having an aromatic group and an anionic dye is used. A method using a dye having a multivalent charge described, a method using a dye having a pyridinium group described in JP-A-10-104774,
JP-A-10-186559 discloses a method using a dye having a hydrophobic group, and JP-A-10-19798.
It has already been found that dye chromophores can be adsorbed on silver halide grains even more by the method using a dye having a coordination bonding group described in No. 0 or the like. However, the sensitizing dyes used in these methods are dyes with a limited structure, and enabling dyes with other structures to enable multilayer adsorption expands the range of this technology and further increases sensitivity. It is what is desired to aim.

[0013]

SUMMARY OF THE INVENTION An object of the present invention is to provide a silver halide light-sensitive material having a high sensitivity, in which grain aggregation is suppressed, a silver halide emulsion therefor, and a sensitizing dye necessary for the emulsion. It is in.

[0014]

According to the present invention, a dye multilayer adsorption structure can be formed by using a betaine dye as a spectral sensitizing dye to be used. A silver photosensitive material, and a silver halide emulsion and a sensitizing dye therefor can be provided. That is, the following (1) to (9) achieve the object of the present invention. (1) In a silver halide photographic emulsion containing silver halide grains having a spectral absorption maximum wavelength of less than 500 nm and a light absorption intensity of 60 or more, or a spectral absorption maximum wavelength of 500 nm or more and a light absorption intensity of 100 or more, the emulsion At least one of the sensitizing dyes used to spectrally sensitize has no charge in the molecule, or forms an intramolecular salt, the molecule has no charge as a whole, and A silver halide photographic emulsion characterized by being a dye having at least one aromatic ring. (2) The silver halide photographic emulsion according to (1), wherein the sensitizing dye is a compound represented by the following general formula (I). General formula (I)

[0015]

Embedded image

In the general formula (I), Z1 and Z2 represent an atom group necessary for forming a 5- or 6-membered nitrogen-containing heterocyclic ring.
However, these may be condensed with a ring. R1 and R2 represent an alkyl group, an aryl group, or a heterocyclic group;
At least one of R2 is a group containing at least one aromatic ring. L1, L2, L3, L4, L5, L
6, and L7 each represent a methine group. p1 and p2 represent 0 or 1. n1 represents 0, 1, 2, or 3. However, the dye represented by the general formula (I) has at least one anionic substituent required for forming an inner salt,
The molecule has no charge as a whole. (3) In the silver halide photographic emulsion described in (1) or (2), when the maximum value of the spectral absorption by the sensitizing dye of the emulsion is defined as Amax, the shortest wavelength indicating the maximum of 80% of Amax and the shortest wavelength. The wavelength interval between the long wavelengths is 20 nm or more, and the wavelength interval between the shortest wavelength and the longest wavelength which indicates 50% of Amax is 12 nm.
The silver halide photographic emulsion according to (1) or (2), which has a thickness of 0 nm or less. (4) In the silver halide photographic emulsion according to (1) or (2), when the maximum value of the spectral sensitivity by the sensitizing dye of the emulsion is defined as Smax, the shortest wavelength and the longest wavelength exhibiting 80% of Smax. The wavelength interval of the wavelength is 20 nm or more, and Smax of 5
The wavelength interval between the shortest wavelength and the longest wavelength indicating 0% is 120.
(1) The silver halide photographic emulsion according to (1) or (2), wherein the longest wavelength showing a spectral absorption of 50% of Amax is from 460 nm to 510 nm, or from 560 nm to 61.
The silver halide photographic emulsion according to (3), wherein the emulsion has a thickness of 0 nm or a range of 640 nm to 730 nm. (6) The longest wavelength showing a spectral sensitivity of 50% of Smax is 4
60 nm to 510 nm, or 560 nm to 610
(4) The silver halide photographic emulsion according to (4), wherein the emulsion has a wavelength of from 640 nm to 730 nm. (7) In a silver halide photographic light-sensitive material containing at least one silver halide photographic emulsion layer,
A silver halide photographic light-sensitive material comprising the silver halide photographic emulsion according to any one of (6). (8) In the compound represented by the above general formula (I), R1,
A compound represented by the general formula (I), wherein R2 is a group containing at least one aromatic ring. (9) A silver halide photographic material comprising at least one compound as described in (8).

[0017]

DESCRIPTION OF THE PREFERRED EMBODIMENTS The details of the present invention will be described below. The present invention is a silver halide photographic emulsion using silver halide grains sensitized by a dye, wherein the silver halide photographic emulsion has a large light absorption intensity and an appropriate spectral absorption waveform and sensitivity distribution. It is a photosensitive material.

In the present invention, the light absorption intensity is the light absorption area intensity by the sensitizing dye per unit particle surface area,
The optical density Log when the amount of light incident on the unit surface area of the particles is I ₀ and the amount of light absorbed by the sensitizing dye on the surface is I.
(I ₀ / (I ₀ −I)) is defined as a value integrated with respect to the wave number (cm ⁻¹ ). Integration range from 5000 cm ^-1 to 35
Up to 000 cm ^-1 .

The silver halide photographic emulsion according to the present invention has a light absorption intensity of 100 or more and a spectral absorption maximum wavelength of 50 for grains having a spectral absorption maximum wavelength of more than 500 nm.
In the case of grains having a size of 0 nm or less, silver halide grains having a light absorption intensity of 60 or more are を of the total projected area of the silver halide grains.
It is preferable to include the above. In addition, the spectral absorption maximum wavelength is 5
In the case of particles exceeding 00 nm, the light absorption intensity is preferably 150 or more, more preferably 170 or more, particularly preferably 200 or more, and the spectral absorption maximum wavelength is 50 or more.
In the case of particles having a size of 0 nm or less, the light absorption intensity is preferably 90 or more, more preferably 100 or more, and particularly preferably 120 or more. There is no particular upper limit, but preferably 2
000 or less, more preferably 1000 or less, particularly preferably 500 or less. In addition, the spectral absorption maximum wavelength is 50
For particles below 0 nm, the spectral absorption maximum wavelength is 35
It is preferably 0 nm or more.

As an example of a method for measuring the light absorption intensity,
Can use a microspectrophotometer.
You. Microspectrophotometer measures the absorption spectrum of a small area
Device that can measure the transmission spectrum of a single particle.
Noh. Of the absorption spectrum of one particle by microspectroscopy
For the measurement, see Yamashita et al.'S report (The Photographic Society of Japan, 199
6th Annual Meeting Abstracts, p. 15)
Can be. From this absorption spectrum, the absorption per particle
Although light intensity is required, the light passing through the particles is
Absorbed on two sides of the surface
Absorption intensity per particle obtained by the method described above.
It can be obtained as の of the yield strength. At this time,
The interval for integrating the absorption spectrum is
5000cm ^-1From 35000cm^-1But on the experiment
Is 500 cm before and after the section with absorption by the sensitizing dye^-1About
It may be the integral of the section including the degree. Also, using microspectroscopy
Even if there is no particle, arrange the particles so that they do not overlap,
It is also possible to measure by measuring the torque. Further light absorption
The intensity is the oscillator strength of the sensitizing dye and the amount of adsorption per unit area.
This is a value uniquely determined by the number of molecules, and is a sensitizing dye oscillator.
If the strength, dye adsorption amount and particle surface area are determined, the light absorption intensity
It can be converted to degrees. The oscillator strength of the sensitizing dye is
Absorption area intensity of sensitizing dye solution (optical density x cm^-1)
It can be obtained experimentally as an example value, so 1M
The absorption area intensity of the dye per area is represented by A (optical density × c
m^-1), The amount of sensitizing dye adsorbed to B (mol / molA)
g) and the particle surface area is C (m^Two/ Mol Ag)
If the light absorption intensity is within the range of about 10% error by the following equation,
You can ask. 0.156 × A × B / C Even if the light absorption intensity is calculated from this equation, it is based on the above-mentioned definition.
The light absorption intensity (Log (I₀/ (I₀−
I)) is the wave number (cm^-1) Is effectively integrated with)
The same value is obtained.

As a method of increasing the light absorption intensity, there are a method of adsorbing the dye chromophore more than once on the particle surface, a method of increasing the molecular extinction coefficient of the dye, and a method of reducing the dye occupation area. Either method may be used, but a method is preferred in which the dye chromophore is adsorbed on the particle surface more than once. Here, the state in which the dye chromophore is adsorbed on the grain surface more than one means that there is more than one dye bound in the vicinity of the silver halide grains, and does not include the dye present in the dispersion medium. Even when the dye chromophore is covalently linked to the substance adsorbed on the particle surface, the effect of increasing the light absorption intensity is long when the linking group is long and the dye chromophore is present in the dispersion medium. Small, not considered more than adsorption. In so-called multilayer adsorption, in which a dye chromophore is adsorbed more than once on the grain surface, it is necessary that spectral sensitization is caused by a dye that is not directly adsorbed on the grain surface. It is necessary to transfer the excitation energy from the non-adsorbed dye to the dye directly adsorbed on the particles. Therefore, if the transmission of the excitation energy needs to occur in more than 10 steps, the final transmission efficiency of the excitation energy becomes low, which is not preferable. One example is disclosed in
Most of the dye chromophores, such as polymer dyes such as 113239, are present in the dispersion medium and the transfer of excitation energy is 1%.
There are cases where zero or more steps are required. In the present invention, the number of coloring steps per molecule is preferably from 1 to 3.

The chromophore described herein means an atomic group that mainly causes the absorption band of a molecule described in the Dictionary of Physical and Chemical Sciences (4th edition, Iwanami Shoten, 1987), pp.985-986. Any atomic group is possible, such as an atomic group having an unsaturated bond such as C = C and N = N.

For example, cyanine dyes, styryl dyes, hemicyanine dyes, merocyanine dyes, trinuclear merocyanine dyes, tetranuclear merocyanine dyes, rhodacyanine dyes, complex cyanine dyes, complex merocyanine dyes, allopolar dyes, oxonol dyes, hemioxonol dyes, squarium Dye, croconium dye,
Azamethine dye, coumarin dye, arylidene dye, anthraquinone dye, triphenylmethane dye, azo dye, azomethine dye, spiro compound, metallocene dye,
Fluorenone dye, fulgide dye, perylene dye, phenazine dye, phenothiazine dye, quinone dye, indigo dye, diphenylmethane dye, polyene dye, acridine dye, acridinone dye, diphenylamine dye,
Examples include quinacridone dyes, quinophthalone dyes, phenoxazine dyes, phthaloperylene dyes, porphine dyes, chlorophyll dyes, phthalocyanine dyes, and metal complex dyes.

Preferably, cyanine dyes, styryl dyes,
And polymethine chromophores such as hemicyanine dyes, merocyanine dyes, trinuclear merocyanine dyes, tetranuclear merocyanine dyes, rhodacyanine dyes, allopolar dyes, and the like. More preferred are cyanine dyes, merocyanine dyes and rhodacyanine dyes, particularly preferred are cyanine dyes and merocyanine dyes, and most preferred are cyanine dyes.

For details of these dyes, see FM Harmer, "Heterocyclic Compounds-Cyanine Soybeans and Related Products".
Compounds (Heterocyclic Compounds-Cyanine Dyes a
nd Related Compounds), John Wiley & Sons, New York, London, 1964, and D.M.
M. Sturmer), Heterocyclic Compounds-Special topics in Heterocyclic Compounds-Special topics i
n heterocyclic chemistry) ", Chapter 18, Section 14,
No. 482 to 515, etc. The general formulas of cyanine dyes, merocyanine dyes and rhodacyanine dyes are described in U.S. Pat. No. 5,340,694 at columns 21-22.
Those shown in (XI), (XII) and (XIII) are preferred.
However, the number of n12, n15, n17, and n18 is not limited and is an integer of 0 or more.

The adsorption of the dye chromophore to the silver halide grains is preferably at least 1.5 layers, more preferably 1.7 layers.
More than two layers, particularly preferably two or more layers. Although there is no particular upper limit, the number is preferably 10 or less, more preferably 5 or less.

In the present invention, the state where one or more chromophores are adsorbed on the surface of the silver halide grains means that among the sensitizing dyes added to the emulsion, the dye having the smallest area occupied by the dye on the surface of the silver halide grains is reached. The saturated adsorption amount per unit surface area is defined as a more saturated coating amount, and the amount of adsorption of the dye chromophore per unit area is larger than the one more saturated coating amount. The number of adsorbed layers means the amount of adsorption based on the amount of one-layer saturated coating. Here, in the case of a dye in which a dye chromophore is linked by a covalent bond, the dye occupied area of each dye in a non-linked state can be used as a reference. The dye occupied area can be determined from an adsorption isotherm showing the relationship between the concentration of free dye and the amount of adsorbed dye, and the particle surface area.
Adsorption isotherms are described, for example, by A. Herz et al. In Adsorption from Aqueous.
s Solution) Advances in Chemistry Series (Advanceds in Chem)
No.try Series) No. 17 and 173 (1968).

The amount of the sensitizing dye adsorbed on the emulsion particles was determined by separating the emulsion adsorbed with the dye into a centrifugal separator to separate the emulsion particles and the supernatant aqueous gelatin solution, and measuring the unadsorbed dye concentration by measuring the spectral absorption of the supernatant. Method to determine the amount of adsorbed dye by subtracting it from the amount of dye added, and drying the precipitated emulsion particles, dissolving a fixed weight of the precipitate in a 1: 1 mixture of aqueous sodium thiosulfate and methanol, and measuring the spectral absorption Can be used to determine the amount of adsorbed dye. When a plurality of types of sensitizing dyes are used, the adsorption amount of each dye can be determined by a technique such as high performance liquid chromatography. A method for determining the amount of dye adsorbed by quantifying the amount of dye in the supernatant is described in, for example, Journal of Physical Chemistry (W. West) et al.
Physical Chemistry) Vol. 56, 1
054 (1952). However, under conditions where the amount of dye added is large, even unadsorbed dye may precipitate, and the method of quantifying the dye concentration in the supernatant may not always obtain the correct amount of dye. On the other hand, if the method of measuring the amount of dye adsorbed by dissolving the precipitated silver halide particles, the emulsion particles have an overwhelmingly high sedimentation speed, so that the particles can be easily separated from the sedimented dye, and the dye adsorbed on the particles can be easily separated. Only the quantity can be measured accurately. This method is the most reliable as a method for obtaining the dye adsorption amount. As an example of a method for measuring the surface area of silver halide grains, a transmission electron micrograph is taken by a replica method,
There is a method of calculating and calculating the shape and size of each particle.
In this case, the thickness of the tabular grains is calculated from the length of the shadow of the replica. Examples of a method for taking a transmission electron micrograph include, for example, “Electron Microscope Sample Techniques”, edited by Kanto Chapter of the Japan Electron Microscope Society, published by Seikado Shinkosha in 1970, Butterworths, London, 1965, P.B. Hirsch (P.B.
Hirsch et al. Electron microscope
Of Chin Crystal (Electron Micr)
oscopy of ThinCrystals).

Other methods include, for example, the journals of AM Kragin et al.
Of Photographic Science (The Jo
urnal of Photographic Sci
ence, Vol. 14, p. 185 (1966), Transactions of the Fara of JF Paddy's Transactions of the Faraday
day Society, Vol. 60, page 1325 (1
964), S. Boyer et al., Journal de Chimie Ph.
ysique et de Physicochimi
e biologice, Vol. 63, p. 1123 (1963), W. Wes
t) et al. of Journal of Physical Chemistry
Istry) Volume 56, 1054 pages (1952)
), H. Sauvenier
r) Editing, E. Klein et al. International Colloquium (International)
al Coloquium), Liege (Lieg)
e), 1959, "Scientific Photograph.
hy)) can be referred to.

The area occupied by the dye is determined experimentally for each case by the above method. However, since the molecular occupation area of a sensitizing dye generally used is approximately 80 A ^{2, the} occupied area of all dyes is simply determined. It is also possible to estimate the approximate number of adsorption layers by setting the area to 80 A ² .

In the present invention, when the dye chromophore is adsorbed in multiple layers on the silver halide grains, the so-called first-layer dye chromophore and the dyes in the second and higher layers are directly adsorbed on the silver halide grains. The reduction potential and oxidation potential of the chromophore may be any, but the reduction potential of the dye chromophore of the first layer is 2 or less.
It is preferable that the dye is noble than a value obtained by subtracting 0.2 from the value of the reduction potential of the dye chromophore of the layer or higher.

Although various methods can be used for measuring the reduction potential and the oxidation potential, preferably, the measurement is performed by phase discrimination type second harmonic AC polarography, and accurate values can be obtained. The method for measuring the oxidation potential by the above-mentioned phase-differential second-harmonic AC polarography is described in Journal of Imaging Science (Jour).
nal of Imaging Science), vol. 30, p. 27 (1986).

The dye chromophore of the second or higher layer is preferably a luminescent dye. As the kind of the luminescent dye, those having a skeleton structure of the dye used for the dye laser are preferable. These are described, for example, in Mitsuo Maeda, Laser Research, 8, 694, 803, 958 (1980) and 9, 85 (1981), and by F. Sehaefer,
"Dye Lasers", arranged in Springer (1973).

Further, it is preferable that the absorption maximum wavelength of the dye chromophore of the first layer in the silver halide photographic light-sensitive material is longer than the absorption maximum wavelength of the dye chromophore of the second layer or more. Further, it is preferable that the emission of the dye chromophore of the second layer or more overlaps with the absorption of the dye chromophore of the first layer. Also, 1
The dye chromophore in the layer preferably forms a J-aggregate. Further, in order to have absorption and spectral sensitivity in a desired wavelength range, it is preferable that the dye chromophore of the second layer or more also forms a J-aggregate.

The meanings of the terms used in the present invention are described below. Dye occupied area: occupied area per dye molecule. It can be determined experimentally from the adsorption isotherm. In the case of a dye to which a dye chromophore is linked by a covalent bond, the dye occupied area of each dye in an unlinked state is used as a reference. 80 for simplicity
A ^2. Saturated coating amount: The amount of dye adsorbed per unit particle surface area at the time of one-saturated coating. Reciprocal of the smallest dye occupied area among the added dyes. Multilayer adsorption: A state in which the amount of dye chromophore adsorbed per unit particle surface area is even larger than the saturated coating amount. Number of adsorbed layers: The amount of dye chromophore adsorbed per unit particle surface area based on the amount of one-layer saturated coating.

The maximum value Amax of the spectral absorptivity and the maximum value Smax of the spectral sensitivity of the emulsion containing silver halide photographic emulsion grains having a light absorption intensity of 100 or more by the sensitizing dye are 5 respectively.
The interval between the shortest wavelength and the longest wavelength indicating 0% is preferably 100 nm or less. 80% of Amax and Smax
The interval between the shortest wavelength and the longest wavelength is 20 nm or more, preferably 100 nm or less, more preferably 80 nm or less.
nm or less, particularly preferably 50 nm or less. Also Am
The interval between the shortest wavelength and the longest wavelength indicating 20% of ax and Smax is preferably 180 nm or less, more preferably 150 nm or less, particularly preferably 120 nm or less, and most preferably 100 nm or less.

The maximum wavelength of spectral absorption is less than 500 nm and the light absorption intensity is 60 or more, or the maximum wavelength of spectral absorption is 500 n
As a preferable method for realizing silver halide grains having a light absorption intensity of 100 or more and a light absorption intensity of 100 or more, there is no charge in the molecule, or an intramolecular salt is formed, and the molecule has no charge as a whole and The present invention discloses a method using a dye having at least one or more aromatic rings. Examples of the aromatic ring include an aromatic hydrocarbon ring, a condensed polycyclic aromatic hydrocarbon ring, and an aromatic heterocyclic ring, and these may be further substituted with the above-described substituent V or the like, May be formed. Preferably, the aromatic ring is benzene,
Naphthalene, anthracene, phenanthrene, fluorene, triphenylene, naphthacene, biphenyl, pyrrole, furan, thiophene, imidazole, oxazole, thiazole, pyridine, pyrazine, pyrimidine, pyridazine, indolizine, indole, benzofuran,
Benzothiophene, isobenzofuran, quinolidine, quinoline, phthalazine, naphthyridine, quinoxaline, quinoxazoline, cinolin, carbazole, phenanthridine, acridine, phenanthroline, thianthrene,
Chromene, xanthene, phenoxatiin, phenothiazine, phenazine and the like.

As the pigment, spiro compounds, metallocenes,
Fluorenone, fulgide, imidazole, perylene, phenazine, phenothiazine, polyene, azo, disazo, quinone, indigo, diphenylmethane, triphenylmethane, polymethine, acridine, acridinone, carbostyril, coumarin, diphenylamine, quinacridone, quinophthalone, phenoxazine, xanthene, Examples include compounds such as acridine, oxazine, thiazine, phenoxazine, phthaloperylene, porphine, chlorophyll, phthalocyanine, squarium, diazobenzene, and bipyridine metal complexes. Preferably, compounds such as azo, diphenylmethane, triphenylmethane, polymethine, porphine, phthalocyanine, squarium, and bipyridine metal complex are exemplified. More preferably, it is polymethine.

As the polymethine dye, any dye can be used. Preferably, cyanine dye, merocyanine dye, rhodocyanine dye, oxonol dye, trinuclear merocyanine dye, tetranuclear merocyanine dye, allopolar dye, styryl dye, styryl base dye, Hemicyanine dyes, streptocyanine dyes, hemioxonol dyes, and the like. Preferred are cyanine dyes, merocyanine dyes and rhodacyanine dyes, and more preferred are cyanine dyes (betaine state as charge). For a detailed description of these dyes, see FM Harmer, Heterocyclic Compounds-Cyanine Dyes and Relatized Compounds.
ed Compounds) ", John Willie and Sons
(John Wiley & Sons)-New York, London, 1
964, and DMSturme
r), Heterocyclic Compounds-Special topics in heterotopic chemistry
cyclic chemistry) ", Chapter 18, Section 14, 482
To 515, etc.

The dye of the formula (I) is particularly preferably a cyanine dye having a basic nucleus condensed with three or more rings. The basic nucleus condensed with three or more rings may be any basic polynuclear condensed heterocyclic nucleus condensed with three or more rings, but is preferably a tricyclic condensed heterocyclic ring,
And 4-cyclic fused ring heterocycles. Preferably, the tricyclic fused ring heterocycle is naphtho [2,3-d] oxazole, naphtho [1,2-d] oxazole, naphtho [2,1-d] oxazole, naphtho [2,3-d] thiazole , Naphtho [1,2-d] thiazole, naphtho [2,1-d] thiazole, naphtho [2,3-d] imidazole, naphtho [1,2-d] imidazole, naphtho [2,1-
d] imidazole, naphtho [2,3-d] selenazole, naphtho
[1,2-d] selenazole, naphtho [2,1-d] selenazole,
Indolo [5,6-d] oxazole, indolo [6,5-d] oxazole, indolo [2,3-d] oxazole, indolo
[5,6-d] thiazole, indolo [6,5-d] thiazole, indolo [2,3-d] thiazole, benzofuro [5,6-d] oxazole, benzofuro [6,5-d] oxazole, benzofuro
[2,3-d] oxazole, benzofuro [5,6-d] thiazole, benzofuro [6,5-d] thiazole, benzofuro [2,3-
d] thiazole, benzothieno [5,6-d] oxazole,
Benzothieno [6,5-d] oxazole, benzothieno [2,3
-d] oxazole and the like. Further, as the tetracyclic condensed heterocyclic ring, preferably anthra [2,3-d] oxazole, anthra [1,2-d] oxazole, anthra [2,1-d]
Oxazole, anthra [2,3-d] thiazole, anthra
[1,2-d] thiazole, phenanthro [2,1-d] thiazole, phenanthro [2,3-d] imidazole, anthra [1,2
-d] Imidazole, anthra [2,1-d] imidazole, anthra [2,3-d] selenazole, phenanthro [1,2-d] selenazole, phenanthro [2,1-d] selenazole, carbazolo [2,3] -d] Oxazole, carbazolo [3,2-d] oxazole, dibenzofuro [2,3-d] oxazole, dibenzofuro [3,2-d] oxazole, carbazolo [2,3-d] thiazole, carbazolo [3,2 -d] Thiazole, dibenzofuro
[2,3-d] thiazole, dibenzofuro [3,2-d] thiazole, benzofuro [5,6-d] oxazole, dibenzothieno
[2,3-d] oxazole, dibenzothieno [3,2-d] oxazole, tetrahydrocarbazolo [6,7-d] oxazole, tetrahydrocarbazolo [7,6-d] oxazole, dibenzothieno [2,3-d ] Thiazole, dibenzothieno [3,2
-d] thiazole, tetrahydrocarbazolo [6,7-d] thiazole and the like. More preferably, the basic nucleus condensed with three or more rings is naphtho [2,3-d] oxazole, naphtho [1,2-d] oxazole, naphtho [2,1-d] oxazole, naphtho [2,3- d] thiazole, naphtho [1,2-d] thiazole, naphtho [2,1-d] thiazole, indolo [5,6-d] oxazole, indolo [6,5-d] oxazole, indolo
[2,3-d] oxazole, indolo [5,6-d] thiazole,
Indolo [2,3-d] thiazole, benzofuro [5,6-d] oxazole, benzofuro [6,5-d] oxazole, benzofuro [2,3-d] oxazole, benzofuro [5,6-d] thiazole, Benzofuro [2,3-d] thiazole, benzothieno [5,6
-d] Oxazole, anthra [2,3-d] oxazole, anthra [1,2-d] oxazole, anthra [2,3-d] thiazole, anthra [1,2-d] thiazole, carbazolo [2,3 -
d] oxazole, carbazolo [3,2-d] oxazole,
Dibenzofuro [2,3-d] oxazole, dibenzofuro [3,2
-d] oxazole, carbazolo [2,3-d] thiazole, carbazolo [3,2-d] thiazole, dibenzofuro [2,3-d] thiazole, dibenzofuro [3,2-d] thiazole, dibenzothieno [2,3] -d] Oxazole, dibenzothieno [3,2-d]
Oxazole, and particularly preferably naphtho.
[2,3-d] oxazole, naphtho [1,2-d] oxazole,
Naphtho [2,3-d] thiazole, indolo [5,6-d] oxazole, indolo [6,5-d] oxazole, indolo [5,6-
d] Thiazole, benzofuro [5,6-d] oxazole, benzofuro [5,6-d] thiazole, benzofuro [2,3-d] thiazole, benzothieno [5,6-d] oxazole, carbazolo [2,3- d] oxazole, carbazolo [3,2-d] oxazole, dibenzofuro [2,3-d] oxazole, dibenzofuro [3,2-d] oxazole, carbazolo [2,3-d] thiazole, carbazolo [3,2- d] Thiazole, dibenzofuro [2,3
-d] thiazole, dibenzofuro [3,2-d] thiazole, dibenzothieno [2,3-d] oxazole, dibenzothieno
[3,2-d] Oxazole.

However, the above-mentioned dye must be in a betaine state in which an inner salt has been formed, or have no charge originally. As a substituent necessary to form an inner salt and neutralize the charge in the molecule, any anionic substituent,
A cationic substituent may be used, but preferred examples include the following. Examples of the anionic substituent include a proton-dissociable acidic group dissociated by 90% or more at a pH of 6 to 8. For example, a sulfo group, a carboxyl group, a phosphate group, and a borate group are mentioned. More preferred are a sulfo group and a carboxyl group. The cationic substituent includes a quaternary ammonium group. Although a plurality of these anionic and cationic substituents may be present in the molecule, the dye molecule as a whole must be uncharged and neutral.

The spectral absorption of the dye adsorbed in the second layer can be determined by subtracting the spectral absorption of the first dye from the overall spectral absorption of the emulsion. Spectral absorption by the first-layer dye can be determined by measuring the absorption spectrum when only the first-layer dye is added. Further, by adding a dye desorbing agent to the emulsion in which the sensitizing dye is adsorbed in multiple layers to desorb the second-layer dye, the spectral absorption spectrum of the first-layer dye can also be measured. In experiments in which the dye is desorbed from the particle surface using a dye desorbing agent, the first-layer dye is usually desorbed after the second-layer dye is desorbed, so if appropriate desorption conditions are selected,
The spectral absorption of the first-layer dye can be determined. This makes it possible to determine the spectral absorption of the second-layer dye. A method using a depigmenting agent is described in a report by Asanuma et al. (Journal of Physical Chemistry B (Jour)
nal of Physical Chemistry
B) Vol. 101, pp. 2149 to 2153 (1997)
Year)) can be referred to.

Hereinafter, the sensitizing dye represented by formula (I) will be described in detail.

In the general formula (I), Z1 and Z2 represent an atom group necessary for forming a nitrogen-containing heterocyclic ring. However, these may be fused with an aromatic ring. The aromatic ring may be a benzene ring, a naphthalene ring or the like, or a heteroaromatic ring such as a pyrazine ring or a thiophene ring. As the nitrogen-containing heterocycle, a thiazoline nucleus, a thiazole nucleus, a benzothiazole nucleus,
An oxazoline nucleus, an oxazole nucleus, a benzoxazole nucleus, a selenazoline nucleus, a selenazole nucleus, a benzoselenazole nucleus, a 3,3-dialkylindolenine nucleus (for example, 3,3-dimethylindolenine), an imidazoline nucleus, an imidazole nucleus, and a benzimidazole nucleus; 2-pyridine nucleus, 4-pyridine nucleus, 2-quinoline nucleus, 4-quinoline nucleus, 1-isoquinoline nucleus, 3-isoquinoline nucleus, imidazo [4,5-b] quinoxalin nucleus, oxadiazole nucleus, thiadiazole nucleus, tetrazole A nucleus, a pyrimidine nucleus and the like can be mentioned, and preferably a benzothiazole nucleus, a benzoxazole nucleus, a 3,3-dialkylindolenine nucleus (for example, 3,3-dimethylindolenine), a benzimidazole nucleus, a 2-pyridine nucleus, 4-pyridine nucleus, 2-quinoline nucleus, 4 Quinoline nucleus, 1-isoquinoline nucleus, a 3-isoquinoline nucleus, more preferably a benzothiazole nucleus, benzoxazole nucleus, 3,
3-dialkylindolenine nucleus (for example, 3,3-dimethylindolenine) and benzimidazole nucleus, particularly preferably benzoxazole nucleus, benzothiazole nucleus and benzimidazole nucleus, most preferably benzoxazole nucleus and benzothiazole nucleus It is.

Assuming that the substituent on these nitrogen-containing heterocycles is V, the substituent represented by V is not particularly limited.
For example, a halogen atom (for example, chlorine, bromine, iodine, fluorine), a mercapto group, a cyano group, a carboxy group, a phosphate group, a sulfo group, a hydroxy group, having 1 to 10 carbon atoms, preferably 2 to 8 carbon atoms, Preferably, a carbamoyl group having 2 to 5 carbon atoms (eg, methylcarbamoyl, ethylcarbamoyl, morpholinocarbonyl), a sulfamoyl group having 0 to 10, preferably 2 to 8, more preferably 2 to 5 carbon atoms (eg, Methylsulfamoyl, ethylsulfamoyl, piperidinosulfonyl), a nitro group, an alkoxy group having 1 to 20, preferably 1 to 10, and more preferably 1 to 8 carbon atoms (for example, methoxy, ethoxy, 2-methoxyethoxy, 2-phenylethoxy), having 6 to 20 carbon atoms, preferably 6 carbon atoms Et 12, more preferably an aryloxy group having 6 to 10 carbon atoms (e.g., phenoxy, p- methylphenoxy, p- chlorophenoxy, naphthoxy),

An acyl group having 1 to 20 carbon atoms, preferably 2 to 12 carbon atoms, more preferably 2 to 8 carbon atoms (eg, acetyl, benzoyl, trichloroacetyl), 1 to 20 carbon atoms, preferably 2 to 20 carbon atoms 12, more preferably an acyloxy group having 2 to 8 carbon atoms (eg, acetyloxy, benzoyloxy);
It preferably has 2 to 12 carbon atoms, and more preferably 2 carbon atoms.
To 8 acylamino groups (eg, acetylamino), 1 to 20, preferably 1 to 10, more preferably 1 to 8 carbon atoms, sulfonyl groups (eg, methanesulfonyl, ethanesulfonyl, benzenesulfonyl), 1 to 20, preferably 1 to 1 carbon atoms
0, more preferably a sulfinyl group having 1 to 8 carbon atoms (for example, methanesulfinyl, ethanesulfinyl, benzenesulfinyl), a sulfonylamino group having 1 to 20 carbon atoms, preferably 1 to 10 carbon atoms, and more preferably 1 to 8 carbon atoms. Groups (eg, methanesulfonylamino, ethanesulfonylamino, benzenesulfonylamino),

An amino group, a substituted amino group having 1 to 20 carbon atoms, preferably 1 to 12 carbon atoms, more preferably 1 to 8 carbon atoms (eg, methylamino, dimethylamino, benzylamino, anilino, diphenylamino); An ammonium group having a number of 0 to 15, preferably 3 to 10 carbon atoms, more preferably 3 to 6 carbon atoms (for example, trimethylammonium, triethylammonium);
To 15, preferably 1 to 10 carbon atoms, more preferably 1 to 6 carbon atoms, such as a trimethylhydrazino group, 1 to 15 carbon atoms, preferably 1 carbon atoms.
To 10, more preferably a ureido group having 1 to 6 carbon atoms (e.g., a ureido group, an N, N-dimethylureido group);
C1 to C15, preferably C1 to C10, more preferably C1 to C6 imide group (for example, succinimide group), C1 to C20, preferably C1 to C12, more preferably C1 to C12 1 to 8 alkylthio groups (eg methylthio, ethylthio, propylthio),
An arylthio group having 6 to 20 carbon atoms, preferably 6 to 12 carbon atoms, more preferably 6 to 10 carbon atoms (eg, phenylthio, p-methylphenylthio, p-chlorophenylthio, 2-pyridylthio, naphthylthio), 2 carbon atoms To 20, preferably 2 to 12, more preferably 2 to 8 alkoxycarbonyl groups (eg methoxycarbonyl, ethoxycarbonyl, 2-benzyloxycarbonyl), 6 to 20 carbon atoms, preferably 6 to 20 carbon atoms 12, more preferably 6 to 10 carbon atoms
Aryloxycarbonyl group (for example, phenoxycarbonyl),

An unsubstituted alkyl group having 1 to 18 carbon atoms, preferably 1 to 10 carbon atoms, more preferably 1 to 5 carbon atoms (eg, methyl, ethyl, propyl, butyl), 1 to 18 carbon atoms, preferably A substituted alkyl group having 1 to 10, more preferably 1 to 5 carbon atoms {eg, hydroxymethyl, trifluoromethyl, benzyl, carboxyethyl, ethoxycarbonylmethyl, acetylaminomethyl, and here having 2 to 18 carbon atoms, preferably Unsaturated hydrocarbon groups having 3 to 10 carbon atoms, more preferably 3 to 5 carbon atoms (for example, vinyl group, ethynyl group 1-cyclohexenyl group, benzylidine group, benzylidene group) are also included in the substituted alkyl group. Having 6 to 20 carbon atoms, preferably 6 to 15 carbon atoms, and more preferably 6 to 10 carbon atoms.換又 unsubstituted aryl group (e.g., phenyl, naphthyl, p- carboxyphenyl, p- nitrophenyl, 3,5-dichlorophenyl, p- cyanophenyl, m- fluorophenyl, p- tolyl)

A substituted or unsubstituted heterocyclic group having 1 to 20, preferably 2 to 10, more preferably 4 to 6 carbon atoms (eg, pyridyl, 5-methylpyridyl, thienyl, furyl, morpholino, tetrahydro Furfuryl). In addition, a structure in which an aromatic ring (for example, a benzene ring or a naphthalene ring) is condensed can be used. Further, V may further substitute on these substituents. Preferred substituents are the above-mentioned alkyl groups, aryl groups, alkoxy groups, halogen atoms, aromatic ring condensation, sulfo groups, carboxy groups, and hydroxy groups.

The substituent V on Z ₁ and Z ₂ is more preferably an aryl group, a heterocyclic group, or a fused aromatic ring. Particularly preferred is an aromatic fused ring.

R ₁ and R ₂ are an alkyl group, an aryl group, and a heterocyclic group.
To 18, preferably 1 to 7, particularly preferably 1 to 4, unsubstituted alkyl groups (eg methyl, ethyl, propyl, isopropyl, butyl, isobutyl, hexyl,
Octyl, dodecyl, octadecyl), a substituted alkyl group having 1 to 18, preferably 1 to 7, and particularly preferably 1 to 4 carbon atoms, such as an alkyl group substituted by V as a substituent. Preferably, an aralkyl group (eg, benzyl, 2-phenylethyl), an unsaturated hydrocarbon group (eg, an allyl group), a hydroxyalkyl group (eg, 2-hydroxyethyl, 3-hydroxypropyl), a carboxyalkyl group (eg, 2- Carboxyethyl, 3-carboxypropyl, 4-carboxybutyl, carboxymethyl), alkoxyalkyl group (for example, 2-methoxyethyl, 2- (2-methoxyethoxy) ethyl), aryloxyalkyl group (for example, 2-phenoxyethyl, 2- (1-naphthoxy) ethyl), an alkoxycarbonylalkyl group (eg, ethoxycarbonylmethyl, 2-benzyloxycarbonylethyl),
Aryloxycarbonylalkyl group (eg, 3-phenoxycarbonylpropyl), acyloxyalkyl group (eg, 2-acetyloxyethyl), acylalkyl group (eg, 2-acetylethyl), carbamoylalkyl group (eg, 2-morpholinocarbonylethyl), sulfamoyl Alkyl group (for example, N, N-dimethylcarbamoylmethyl), sulfoalkyl group (for example, 2-sulfoethyl, 3-sulfopropyl, 3-sulfobutyl,
-Sulfobutyl, 2- [3-sulfopropoxy] ethyl, 2-hydroxy-3-sulfopropyl, 3-sulfopropoxyethoxyethyl), sulfoalkenyl group, sulfatoalkyl group (for example, 2-sulfatoethyl group, 3- Sulfatopropyl, 4-sulfatobutyl), heterocyclic-substituted alkyl group (for example, 2- (pyrrolidin-2-one-1-yl) ethyl, tetrahydrofurfuryl), alkylsulfonylcarbamoylmethyl group (for example, methanesulfonylcarbamoylmethyl group) )｝, An unsubstituted aryl group having 6 to 20 carbon atoms, preferably 6 to 10 carbon atoms, more preferably 6 to 8 carbon atoms (eg, phenyl group, naphthyl group), 6 to 20 carbon atoms, preferably A substituted aryl group having 6 to 10, more preferably 6 to 8 carbon atoms (eg, Aforementioned V mentioned as examples of substituents include aryl groups substituted. Specifically p- methoxyphenyl group, p- methylphenyl group, p-
A chlorophenyl group; ), An unsubstituted heterocyclic group having 1 to 20, preferably 3 to 10, more preferably 4 to 8 carbon atoms (eg, 2-furyl, 2-thienyl, 2-pyridyl, 3-pyrazolyl, 3-iso Oxazolyl, 3-isothiazolyl, 2-imidazolyl, 2-oxazolyl, 2-thiazolyl,
-Pyridazyl, 2-pyrimidyl, 3-pyrazyl, 2- (1,3,5-triazolyl), 3- (1,2,4-triazolyl), 5-tetrazolyl), having 1 to 20 carbon atoms, preferably 3 to 10 carbon atoms, More preferably, it is a substituted heterocyclic group having 4 to 8 carbon atoms (for example, a heterocyclic group substituted by V described above as an example of the substituent. More specifically, a 5-methyl-2-thienyl group, a 4-methoxy-2-pyridyl group And the like.).

In formula (I), R ₁ and R ₂ are preferably at least one of R ₁ and R _2.
Represents a group containing two aromatic rings, and the general formula (I) forms an inner salt and has no charge. Therefore, general formula (I) must have at least one anionic group in the molecule. Such anionic groups may be R1 or R
Preferably, it is included in any one of the two. Examples of the aromatic ring in R ₁ and R ₂ include an aromatic hydrocarbon ring, a condensed polycyclic aromatic hydrocarbon ring, and an aromatic heterocyclic ring. And a condensed ring may be formed. Preferred examples of the aromatic ring in R ₁ and R ₂ include benzene, naphthalene, pyrrole, furan, thiophene, pyridine, quinoline and the like.

R ₁ and R ₂ are preferably an aralkyl group (for example, an alkyl group substituted by an aryl group)
Benzyl, 2-phenylethyl, naphthylmethyl, 2-
(4-biphenyl) ethyl), an aryloxyalkyl group (for example, 2-phenoxyethyl, 2- (1-naphthoxy) ethyl, 2- (4-biphenyloxy) ethyl, 2-
(O, m, p-halophenoxy) ethyl, 2- (o,
m, p-methoxyphenoxy) ethyl), an aryloxycarbonylalkyl group (3-phenoxycarbonylpropyl, 2- (1-naphthoxycarbonyl) ethyl), an aralkyl group substituted by a sulfo group, a phosphate group, or a carboxyl group (Eg, 2-sulfobenzyl, 4-sulfobenzyl, 4-sulfophenethyl, 3-phenyl-3
-Sulfopropyl, 3-phenyl-2-sulfopropyl, 4,4-diphenyl-3-sulfobutyl, 2-
(4′-sulfo-4-biphenyl) ethyl, 4-phosphobenzyl), an aryloxycarbonylalkyl group substituted with a sulfo group, a phosphate group, or a carboxyl group (3
-Sulfophenoxycarbonylpropyl), a sulfo group,
An aryloxyalkyl group substituted with a phosphate group or a carboxyl group (for example, 2- (4-sulfophenoxy) ethyl, 2- (2-phosphophenoxy) ethyl,
4,4-diphenoxy-3-sulfobutyl), and the like. Further, as a heterocyclic substituted alkyl group, for example,
2- (pyrrolidin-2-one-1-yl) ethyl, 2-
(2-pyridyl) ethyl, 2- (4-pyridyl) ethyl, 2- (2-furyl) ethyl, 2- (2-thienyl)
Ethyl, 2- (2-pyridylmethoxy) ethyl, 3-
(2-pyridyl) -3-sulfopropyl, 3- (2-furyl) -3-sulfopropyl, 2- (2-thienyl)-
2-sulfopropyl and the like. Examples of the aryl group include 4-methoxyphenyl, phenyl, naphthyl, biphenyl, or an aryl group substituted with a sulfo group, a phosphate group, or a carboxyl group (for example, 4-sulfophenyl, 4-sulfonaphthyl) and the like. As the heterocyclic group, a 2-thienyl group, 4-chloro-2-thienyl, 2-pyridyl, 3-pyrazolyl, or a heterocyclic group substituted with a sulfo group, a phosphoric acid group, or a carboxyl group (for example, a 4-sulfo-2-thienyl group) , 4-sulfo-2-pyridyl group) and the like.

More preferably, the above-mentioned substituted or unsubstituted aryl group or an alkyl group substituted with an aryl group or a heterocyclic group, and an aralkyl group or a sulfo group substituted with a sulfo group, a phosphate group, or a carboxyl group. , A phosphate group, or an aryloxyalkyl group substituted with a carboxyl group.

L ₁ , L ₂ , L ₃ , L ₄ , L ₅ , L ₆ , L
₇ each independently represents a methine group. The methine group represented by L _{1 to} L ₇ may have a substituent. Examples of the substituent include a substituted or unsubstituted C ₁ to C 15, preferably C ₁ to C 10, particularly preferably carbon Numbers 1 through 5
An alkyl group (e.g., methyl, ethyl, 2-carboxyethyl), a substituted or unsubstituted aryl group having 6 to 20, preferably 6 to 15, more preferably 6 to 10 carbon atoms (e.g., phenyl, o-carboxyphenyl), a substituted or unsubstituted heterocyclic group having 3 to 20 carbon atoms, preferably 4 to 15 carbon atoms, more preferably 6 to 10 carbon atoms (for example, N, N-dimethylbarbituric acid group); Halogen atoms (eg, chlorine, bromine, iodine,
Fluorine), an alkoxy group having 1 to 15 carbon atoms, preferably 1 to 10 carbon atoms, more preferably 1 to 5 carbon atoms (eg, methoxy, ethoxy), 0 to 15 carbon atoms, preferably 2 to 10 carbon atoms, Preferably an amino group having 4 to 10 carbon atoms (for example, methylamino, N, N-dimethylamino, N-methyl-N-phenylamino, N-methylpiperazino), 1 to 15 carbon atoms, preferably 1 to 10 carbon atoms; More preferably, it is an alkylthio group having 1 to 5 carbon atoms (eg, methylthio, ethylthio), and 6 carbon atoms.
To 20, preferably 6 to 12 carbon atoms, more preferably 6 to 10 carbon atoms, such as phenylthio and p-methylphenylthio. Further, a ring may be formed with another methine group, or Z ₁ to
A ring can be formed together with Z ₁₃ .

N ₁ represents 0, ₁ , 2, 3 or 4. It is preferably 0, 1, 2, 3, and more preferably 0,
1, 2 and particularly preferably 0, 1. n ₁ is 2
At this point, the methine groups are repeated but need not be the same.

P ₁ and p ₂ each independently represent 0 or 1. Preferably it is 0.

In the present invention, when the dye represented by the general formula (I) is adsorbed on silver halide grains, the dye represented by the general formula (I) exhibits absorption and spectral sensitivity in a desired wavelength range. It is preferable to form a J-aggregate in order to have.

Next, only specific examples of the dyes used in the particularly preferred technology, which have been described in detail in the description of the embodiments of the present invention, are shown below. Of course, the present invention is not limited to these.

Specific examples of the compound represented by formula (I) of the present invention.

[0061]

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[0062]

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[0063]

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[0064]

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[0065]

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[0066]

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[0067]

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[0068]

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[0069]

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[0070]

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[0071]

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[0072]

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[0073]

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[0074]

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[0075]

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[0076]

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[0077]

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The compound represented by the general formula (I) of the present invention is described in "Heterocyclic Compounds-Cyanine Soybean &And" by FM Harmer.
Related Compounds (Heterocyclic Compounds)
-Cyanine Dyes and Related Compounds), John Wiley & Sons, New York, London, 1964, DMSturmer, Heterocyclic Compounds-Special Topics. In Heterocyclic Chemistry
s-Special Topics in Heterocyclic Chemistry) "
Chapter 18, Section 14, pages 482-515, John Wiley & Sons, Inc.-New York, London, 1977, "Rodd's Chess of Carbon Compounds.
mistry of Carbon Compouds) "Second Edition, Volume I
V, Part B, Chapter 15, pages 369-422 Elsevier Science Public Company, Inc.
(Sevier Science Publishing Company Inc.), New York, published in 1977.

In the present invention, in order to incorporate the compound represented by the general formula (I) described above in the silver halide emulsion of the present invention, they may be directly dispersed in the emulsion, or Water, methanol, ethanol, propanol, acetone, methylcellosolve, 2,2,3,3-tetrafluoropropanol, 2,2,2-trifluoroethanol, 3-methoxy-1-propanol, 3-methoxy-
A solvent such as 1-butanol, 1-methoxy-2-propanol, acetonitrile, tetrahydrofuran, N, N-dimethylformamide or the like may be dissolved alone or in a mixed solvent and added to the emulsion. Also, U.S. Pat.
No. 987, etc., a method in which a dye is dissolved in a volatile organic solvent, the solution is dispersed in water or a hydrophilic colloid, and this dispersion is added to an emulsion.
As described in JP-A-24185 and the like, a method of dispersing a water-insoluble dye in a water-soluble solvent without dissolving and adding this dispersion to an emulsion, JP-B-44-23389, JP-B-44-27555, As described in JP-B-57-22091, a method in which a dye is dissolved in an acid and the solution is added to the emulsion, or a solution in which an acid or a base is coexistent to be added as an aqueous solution and added to the emulsion, US Pat. , 822, 135
No. 4,006,025, a method of adding an aqueous solution or colloidal dispersion in the presence of a surfactant to an emulsion,
JP-A-102733, JP-A-58-105141, a method in which a dye is directly dispersed in a hydrophilic colloid, and the dispersion is added to an emulsion.
As described in No. 24, a method in which a dye is dissolved using a compound that causes a red shift, and the solution is added to an emulsion can also be used. Also, ultrasonic waves can be used for dissolution.

The dye may be added in portions or all at once. When the dye is added in portions, the fluorescence yield of the dye added later in the gelatin dry film is preferably It is 0.5 or more, and more preferably 0.8 or more. Further, the reduction potential of the dye added later is equal to or lower than the reduction potential of the dye added earlier, and more preferably 0.03 V or more. The oxidation potential added later is preferably 0.01 V or more lower than the oxidation potential of the dye added earlier, and more preferably 0.03 V or more lower. The dye may be added at any time during the preparation of the emulsion. The temperature at which the dye is added may be any number of times, but the emulsion temperature at the time of adding the dye is preferably from 10 ° C to 75 ° C, particularly preferably from 30 ° C to 65 ° C. The emulsion used in the present invention may be unchemically sensitized,
Preferably, it is chemically sensitized. The total amount of the dye may be added before the chemical sensitization, or may be added after the chemical sensitization.However, the chemical sensitization is preferably performed after a part of the added dye is added, and then the remaining dye is added. Is added to allow more optimal chemical sensitization.

The silver halide emulsion used in the silver halide photographic light-sensitive material of the present invention is not particularly limited as silver halide, and silver chloride, silver chlorobromide, silver bromide, silver iodochloride, and silver iodobromide are used. However, an emulsion containing bromide ions or iodide ions is more preferable. The shape of the silver halide grains may be a regular crystal system (normal crystal grains) or an irregular crystal system. Further, grains having one or more twin planes may be used, and hexagonal tabular grains and triangular tabular grains having two or three parallel twin planes are preferably used. Further, in the case of tabular grains, it is more preferable that the grain size distribution be monodisperse (coefficient of variation: 10 to 20%). Monodisperse hexagonal tabular grains are described in JP-A-63-151618, JP-A-2-838 and European Patent 514,742. Further, the coefficient of variation of the particle thickness is preferably 20% or less, particularly preferably 5 to 15%.

The tabular grains have a principal plane of (10
Nos. 0) and (111) are known. For the former, silver bromide is described in U.S. Pat. No. 4,063,951 and JP-A-5-281640. US Patent 5,
No. 264,337. The latter tabular grains are grains having various shapes having one or more twin planes described above, and silver chloride is disclosed in U.S. Pat. No. 4,399,215.
Nos. 4,983,508 and 5,183,732
And JP-A-3-137632 and JP-A-3-11611.
No. 3 describes it. can do. The present invention can be preferably applied to tabular grains having a main plane of (100) and tabular grains having a main plane of (111). The aspect ratio (equivalent circle diameter / grain thickness) of tabular grains is 2 to
100, preferably 3 to 50, particularly preferably 5 to 30
It is. The equivalent circle diameter of tabular grains is 0.2 to 5.0.
μm, preferably 0.5 to 3.0 μm, particularly preferably 0.6 to 2.0 μm. The thickness of the tabular grains is preferably 0.02 to 0.3 μm, and 0.03 to 0.2 μm.
m is particularly preferred.

The silver halide grains may have dislocation lines in the grains. A technique for introducing dislocations into silver halide grains while controlling the dislocations is disclosed in JP-A-63-22023.
No. 8 describes it. By introducing the dislocation, effects such as an increase in sensitivity, an improvement in storage stability, an improvement in stability of a latent image, and a reduction in pressure fog can be obtained. Thereby, dislocations are mainly introduced into the edge portion of the tabular grain. Further, with respect to tabular grains having dislocations introduced at the center, U.S. Pat.
No. 96 is described. The present invention is effective when 50% or more of the silver halide grains contain 10 or more dislocation lines per grain.

A silver halide solvent can be used to promote growth during the crystal formation process, and to effectively make chemical sensitization effective during grain formation and / or chemical sensitization. As preferred silver halide solvents, water-soluble thiocyanates, ammonia, thioethers and thioureas can be used. Examples of the silver halide solvent include thiocyanates (U.S. Pat.
No. 448534, No. 3320069), ammonia,
Thioether compounds (U.S. Pat.
574628, 3704130, 429743
Nos. 9 and 4276347) and thione compounds (Japanese Patent Application Laid-Open No.
Nos. 3-144319, 53-82408, 55-
No. 77737), amine compounds (JP-A-54-1007)
No. 17), thiourea derivatives (JP-A-55-2982)
No.), imidazoles (JP-A-54-100717)
And substituted mercaptotetrazole (JP-A-57-20)
2531).

The method for producing a silver halide emulsion is not particularly limited. That is, any of an acidic method, a neutral method, an ammonia method and the like may be used, and a method of reacting a soluble silver salt and a soluble halide may be any of a one-sided mixing method, a double-mixing method, a combination thereof, and the like. good.
Further, a method of changing the addition rate of silver nitrate or an aqueous alkali halide solution in accordance with the grain growth rate (UK Patent 1535)
No. 016, JP-B-48-36890 and 52-1
No. 6364) and a method of changing the concentration of an aqueous solution (U.S. Pat. No. 4,242,445 and JP-A-55-158124).
It is preferable to use 早 く to grow the swiftly within a range not exceeding the critical supersaturation degree.

Instead of adding a silver salt solution and a halogen solution to a reaction vessel, a method in which fine particles prepared in advance are added to the reaction vessel to cause nucleation and / or grain growth to obtain silver halide grains. It is also preferred to use According to this method, the distribution of halogen ions in the emulsion grain crystals can be made completely uniform, and favorable photographic characteristics can be obtained. Further, in the present invention,
Emulsion grains having various structures can be used. So-called core / shell double-structure particles composed of particles inside (core portion) and outside (shell portion), triple structure particles (described in Japanese Patent Application Laid-Open No. 60-222844), and multi-layer particles of higher size are used. . When a structure is provided inside the emulsion grain, not only the above-described wrapping structure but also a grain having a so-called junction structure can be produced. These examples are described in JP-A-58-108526 and JP-A-59-1625.
No. 4, No. 59-133540, Japanese Patent Publication No. 58-2577
No. 2 and EP 199 290 A2. In the present invention, it is most preferable to use core-shell type double structure particles.

In the case of silver iodobromide particles having these structures, for example, in core-shell type particles, even if the silver iodide content in the core portion is high and the silver iodide content in the shell portion is low, Conversely, grains having a low silver iodide content in the core portion and a high silver iodide content in the shell portion may be used. The silver halide emulsion is preferably of a surface latent image type. However, JP-A-59-1
As disclosed in Japanese Patent No. 33542, an internal latent image type emulsion can be used by selecting a developing solution or a developing condition. Also, a shallow internal latent image type emulsion covered with a thin shell can be used according to the purpose. Regarding the production method of the silver iodobromide tabular emulsion preferably used in the present invention, US Pat.
No. 4,433,048, No. 4,414,310, No. 5,334,495 and the like can be referred to.
Also, ultra-thin tabular emulsions having a grain thickness of 0.1 μm or less are described in U.S. Pat.
No. 5,418,125, etc. can be referred to. When the present invention is applied to a high silver chloride tabular emulsion, the emulsion preferably used is EP 723187.
No., No. 615517, No. 534395, No. 5
No. 84644 can be referred to.

The silver halide emulsion is generally used after chemical sensitization. As chemical sensitization, chalcogen sensitization (sulfur sensitization, selenium sensitization, tellurium sensitization), noble metal sensitization (eg, gold sensitization), and reduction sensitization are performed alone or in combination. In the present invention, chemical sensitization combining sulfur sensitization and gold sulfur sensitization is preferably used, but selenium sensitization and tellurium sensitization are also preferably used. In sulfur sensitization,
Unstable sulfur compounds are used as sensitizers. Examples of the sulfur sensitizer include thiosulfates (eg, sodium thiosulfate, p-toluenethiosulfonate), thioureas (eg, diphenylthiourea, triethylthiourea, N-ethyl-N ′).
-(4-methyl-2-thiazolyl) thiourea, carboxymethyltrimethylthiourea), thioamides (eg, thioacetamide, N-phenylthioacetamide), rhodanines (eg, rhodanine, N-ethylrhodanine,
5-benzylidene rhodanine, 5-benzylidene-N-
Ethyl-rhodanine, diethylrhodanine), phosphine sulfides (eg, trimethylphosphine sulfide), thiohydantoins, 4-oxo-oxazolidin-2-thiones, dipolysulfides (eg, dimorpholine disulfide, cystine, Hexathiocan-thione), mercapto compounds (eg, cysteine), polythionates and elemental sulfur. Activated gelatin can also be used as a sulfur sensitizer.

In selenium sensitization, an unstable selenium compound is used as a sensitizer. Unstable selenium compounds are described in JP-B-43-13489 and JP-B-44-15748.
No., JP-A-4-25832, JP-A-4-109240,
It is described in JP-A-4-271341 and JP-A-5-40324. Examples of selenium sensitizers include colloidal metal selenium, selenoureas (eg, N, N-dimethylselenourea,
Trifluoromethylcarbonyl-trimethylselenourea, acetyl-trimethylselenourea), selenoamides (eg, selenoacetamide, N, N-diethylphenylselenoamide), phosphine selenides (eg, triphenylphosphine selenide, pentane) Fluorophenyl-triphenylphosphine selenide), selenophosphates (eg, tri-p-tolylselenophosphate, tri-n-butylselenophosphate), selenoketones (eg, selenobenzophenone) isoselenocyanates, Includes selenocarboxylic acids, selenoesters and diacyl selenides. In addition, relatively stable selenium compounds such as selenous acid, potassium selenocyanide, selenazoles and selenides (Japanese Patent Publication No.
Nos. 4553 and 52-34492) can also be used as selenium sensitizers.

In the tellurium sensitizer, an unstable tellurium compound is used as a sensitizer. Unstable tellurium compounds are described in Canadian Patent 800,958, British Patent 1,
295,462, 1,396,696, JP-A-4-204640, JP-A-4-271341, and 4-3
No. 33043 and 5-303157. Examples of tellurium sensitization include telluroureas (eg, tetramethyltellurourea, N, N'-dimethylethylene tellurourea, N, N'-diphenylethylenetellurourea), phosphine tellurides (eg, butyl- Diisopropylphosphine telluride, tributylphosphine telluride,
Tributoxyphosphine telluride, ethoxy-diphenylphosphine telluride), diacyl (di) tellurides (eg, bis (diphenylcarbamoyl) ditelluride,
Bis (N-phenyl-N-methylcarbamoyl) ditelluride, bis (N-phenyl-N-methylcarbamoyl)
Telluride, bis (ethoxycarbonyl) telluride), isotellurocyanates (eg, allyl isotellurocyanate), tellurokenes (eg, telluroacetone, telluroacetophenone), telluramides (eg, telluroacetamide, N, N-dimethyltellurobenzamide) ), Tellurohydrazides (eg, N, N ', N'-trimethyltellurobenzhydrazide), telluroesters (eg, t-butyl-t-hexyltelluroester), colloidal tellurium, (di) tellurides and others Of tellurium compounds (eg,
Potassium telluride, sodium telluropentathionate).

In the noble metal sensitization, a salt of a noble metal such as gold, platinum, palladium or iridium is used as a sensitizer. For precious metal salts, see P. Grafkides, Chimie et P
hysique Photographique (Paul Montel, 1987,
5th edition), Research Disclosure, Vol. 307, 307105
There is a description in the issue. Gold sensitization is particularly preferred. Examples of gold sensitization include chloroauric acid, potassium chloroaurate, potassium aurithiocyanate, gold sulfide, and gold selenide. In addition, U.S. Pat.
The gold compounds described in Nos. 49,484 and 5,049,485 can also be used. As one form of gold sensitization, U.S. Pat. Nos. 5,700,631;
It is also preferable to use the gold complexes described in JP-A-67032 and JP-A-8-69074.

In the present invention, reduction sensitization can be used in combination. Examples of reduction sensitizers include aminoiminomethanesulfinic acid (thiourea dioxide), borane compounds (eg, dimethylamine borane), hydrazine compounds (eg, hydrazine,
p-tolylhydrazine), polyamine compounds (eg, diethylenetriamine, triethylenetetramine), stannous chloride, silane compounds, reductones (eg, ascorbic acid), sulfites, aldehyde compounds and hydrogen. Further, reduction sensitization can be carried out in an atmosphere having a high pH or an excess of silver ions (so-called silver ripening).

The chemical sensitization may be carried out by combining two or more kinds. As the combination, a combination of chalcogen sensitization and gold sensitization is particularly preferable. Further, reduction sensitization is preferably performed at the time of forming silver halide grains. The amount of sensitizer used is
It is determined by the type of silver halide grains generally used and the conditions of chemical sensitization. The amount of the chalcogen sensitizer used is generally 10 ^-8 to 10 ^-2 mol per mol of silver halide,
It is preferably from ^{-7 to} 5 × 10 ^-3 mol. The use amount of the noble metal sensitizer is preferably 10 ^-7 to 10 ^-2 mol per mol of silver halide. There are no particular restrictions on the conditions for chemical sensitization. The pAg is from 6 to 11, preferably from 7 to 10. Preferably, the pH is between 4 and 10. Temperature is 40 ~ 95 ℃
And more preferably 45 to 85 ° C.

The layer constitution of the silver halide photographic material is not particularly limited. However, in the case of color photographic materials, blue,
It has a multilayer structure for recording green and red light separately. Each silver halide emulsion layer may be composed of two layers, a high-speed layer and a low-speed layer. Examples of practical layer configurations are listed in (1) to (6) below.

(1) BH / BL / GH / GL / RH / R
L / S (2) BH / BM / BL / GH / GM / GL / RH / R
M / RL / S (3) BH / BL / GH / RH / GL / RL / S (4) BH / GH / RH / BL / GL / RL / S (5) BH / BL / CL / GH / GL / RH / RL / S (6) BH / BL / GH / GL / CL / RH / RL / S

B is a blue-sensitive layer, G is a green-sensitive layer, R is a red-sensitive layer, H is the highest sensitivity layer, M is an intermediate sensitivity layer, L is a low sensitivity layer, S is a support, and CL is a multilayer effect. Layer. Non-photosensitive layers such as a protective layer, a filter layer, an intermediate layer, an antihalation layer and an undercoat layer are omitted. The high-sensitivity layer and the low-sensitivity layer having the same color sensitivity may be arranged in reverse.
(3) is described in US Pat. No. 4,184,876. For (4), Research Disclos
ure, Vol. 225, No. 22534, JP-A-59-177551
And JP-A-59-177552.
Further, (5) and (6) are described in JP-A-61-345.
No. 41 discloses this. Preferred layer constitutions are (1)
(2) and (4). The silver halide photographic material of the present invention can be applied not only to color photographic materials but also to X-ray photographic materials, black-and-white photographic materials, plate-making photographic materials and photographic paper.

Various additives for the silver halide emulsion (eg, binder, chemical sensitizer, spectral sensitizer, stabilizer, gelatin, hardener, surfactant, antistatic agent, polymer latex, matting agent, colorant For couplers, ultraviolet absorbers, anti-fading agents, dyes), photographic material supports and photographic material processing methods (eg, coating methods, exposure methods, development processing methods), Research Disclosure 176, 17643 (RD- 17643), 187, 18716 (RD-18716),
Reference can be made to the description of Vol. 225, No. 22534 (RD-22534). The following table shows the descriptions in these Research Disclosure magazines.

種類 Additive type RD-17643 RD-18716 RD-22534 ─ ───────────────────────────────── 1 Chemical sensitizer Page 23 648 Right column Page 24 2 Sensitivity enhancer Same as above 3 Spectral sensitizer, page 23-24 page 648, right column 24-28 page Supersensitizer 〜 page 649 right column 4 Brightening agent page 24 5 Anti-fogging agent, page 24-25 page 649 right column page 24 , Page 31 Stabilizer 6 Light absorber, pages 25 to 26, page 649, right column Filter dye, 650 page 650, left column UV absorber Stain inhibitor, page 25, right column 650, left column to right column 8 Dye image stabilizer 25 Page 32 9 Hardener 26 Page 651 Left column 32 Page 10 Binder 26 Same as above 28 Page 11 Plasticizers and lubricants 27 Page 650 Right column 12 Coating aids, pages 26 to 27 Same as above Surfactant 13 Antistatic Agent page 27 Same as above 14 Color coupler page 25 page 649 page 31 ───── ─────────────────────────────

As the gelatin hardener, for example, an active halogen compound (2,4-dichloro-6-hydroxy-
1,3,5-triazine and its sodium salt, etc.)
And active vinyl compounds (such as 1,3-bisvinylsulfonyl-2-propanol, 1,2-bis (vinylsulfonylacetamido) ethane or a vinyl-based polymer having a vinylsulfonyl group in the chain) can rapidly convert hydrophilic colloids such as gelatin. It is preferred because it cures and gives stable photographic properties. N-carbamoylpyridinium salts ((1
-Morpholinocarbonyl-3-pyridinio) matansulfonate) and haloamidinium salts (such as 1- (1-chloro-1-pyridinomethylene) pyrrolidinium 2-naphthalenesulfonate) can be preferably used because of their high curing rate.

Color photographic materials are available from Research Disclosure
Development can be carried out by a usual method described in 176, 17643 and 187, 18716.
The color photographic light-sensitive material is usually subjected to a washing treatment or a stabilizer treatment after development, bleach-fixing or fixing. In the rinsing step, two or more tanks are generally countercurrently washed to save water. As a stabilizing treatment, a multi-stage countercurrent stabilizing treatment as described in JP-A-57-8543 is exemplified instead of the washing step.

In addition to the above, the color coupler used in the present invention is described in JP-A No. 11-65007, paragraphs 0019 to 0024, and the chemical sensitization is described in paragraphs 0041 to 0053 of the same publication. For the agent, paragraph No. 0057 of the same publication, for sensitizing dyes and the like, paragraphs 0058 to 0060 of the same publication, for development processing, paragraphs 0080 to 999 of the same publication, and for the application to the APS system, paragraphs 0100 to 0100 of the same publication. 01
26 can be referred to.

[0102]

EXAMPLES The present invention will be described in more detail with reference to Examples, but the present invention is not limited thereto. <Example 1> Synthesis of compound (S-3) The whole process of the synthesis of compound (S-3) is shown in the following Scheme 1. Scheme 1

[0103]

Embedded image

Synthesis of Compound (S-3-C) A mixture of 10 g of 5-phenyl-2-methylbenzoxazole and 11 g of 1-phenylpropanesultone was mixed at 150 ° C.
For 3 hours. After cooling, 100 ml of ethyl acetate was added, the mixture was stirred at room temperature for 2 hours, and the crystals were collected by filtration and dried to obtain 18.59 g (yield: 95%) of compound (S-3-C). Synthesis of Compound (S-3-A) 10 g of Compound (S-3-C), 10 g of triethylorthopropionic acid, and 10 ml of m-cresol External temperature 100
Stirred at C for 1 hour. After cooling with water, 100 ml of ethyl acetate
And stirred at room temperature for 1 hour, and the resulting crystals are filtered.
By drying under reduced pressure, the compound (S-3-A) 8.1 was obtained.
g (yield: 67%, λmax = 334 nm). Synthesis of Compound (S-3-B) 72 g of 5-phenyl-2-methylbenzoxazole and 100 g of 2-phenoxyethyl tosylate were mixed, and 15
Stirred at 0 ° C. for 8 hours. After cooling, ethyl acetate 400 ml
Was added and the mixture was stirred at room temperature for 2 hours, and the crystals were collected by filtration and dried to obtain 150 g (yield 87%) of compound (S-3-B). Synthesis of Compound (S-3-C) 1.0 g of Compound (S-3-A) and Compound (S-3-A)
B) 30 ml of N, N-dimethylacetamide in 0.91
And stirred at an external temperature of 140 ° C. for 1 hour. After cooling, 100 ml of ethyl acetate and 100 ml of hexane are added and stirred at room temperature to separate an oily substance. This was taken out by decantation and purified by silica gel column chromatography (SiO ₂ : 150 g, dichloromethane / methanol = 20 → 10) to give the compound (S-
3) 0.3 g (Yield: 22% λmax (MeOH) =
505.6 nm, melting point: 232 ° C.). Example 2 Preparation of Pure Silver Bromide Side Plate Grain Emulsion and Silver Iodobromide Tabular Grain Emulsion 6.4 g of potassium bromide and low molecular weight gelatin 6 having an average molecular weight of 15,000 or less in 1.2 liters of water Dissolving 0.2 g and keeping the temperature at 30 ° C. with a 16.4% aqueous silver nitrate solution 8.1.
ml and 7.2 ml of a 23.5% aqueous potassium bromide solution were added by the double jet method over 10 seconds. Next, 11.7
% Gelatin aqueous solution, and heated to 75 ° C.
After aging for 3 minutes, 370 ml of a 32.2% silver nitrate aqueous solution
And a 20% aqueous potassium bromide solution were added over 10 minutes while maintaining the silver potential at -20 mV, and the temperature was lowered to 35 ° C after physical ripening for 1 minute. Thus, the average projected area diameter is 2.32 μm, the thickness is 0.09 μm, and the diameter variation coefficient is 1
A 5.1% monodispersed pure silver bromide tabular emulsion (specific gravity: 1.15) was obtained. Thereafter, soluble salts were removed by the coagulation sedimentation method.
The temperature was again maintained at 40 ° C., and 45.6 g of gelatin and 1 mol
10 ml of an aqueous sodium hydroxide solution having a concentration of
167 ml of water and 10 ml of 5% phenol were added and p
Ag was adjusted to 6.88 and pH to 6.16 to obtain Emulsion A. In the preparation of Emulsion A, an emulsion prepared by using a 20% aqueous potassium bromide solution at the time of tabular grain growth and a mixed aqueous solution of 17% potassium bromide and 3% potassium iodide was used as Emulsion B. Thereafter, potassium thiocyanate, chloroauric acid and sodium thiosulfate were added to the emulsions A and B so as to obtain the optimum sensitivity, and the emulsions were ripened at 55 ° C. for 50 minutes. While maintaining the emulsion thus obtained at 50 ° C., the first dye shown in Table 1 was added, the mixture was stirred at 50 ° C. for 30 minutes, the second dye was added, and the mixture was further stirred at 50 ° C. for 30 minutes.

[0105]

[Table 1]

[0106]

Embedded image

The amount of dye adsorbed was determined as follows.
After centrifugation at 000 rpm for 10 minutes, the precipitate was freeze-dried, and 0.05 g of the precipitate was made up to 50 ml by adding 25 ml of a 25% aqueous sodium thiosulfate solution and methanol. This solution was analyzed by high performance liquid chromatography, and the dye concentration was quantified and determined.

To measure the light absorption intensity per unit area, the obtained emulsion was thinly coated on a slide glass, and the transmittance of each particle was measured by the following method using a microspectrophotometer MSP65 manufactured by Carl Zeiss Co., Ltd. The absorption spectrum was determined by measuring the spectrum and the reflection spectrum. The reference of the transmission spectrum refers to the part without particles,
The reflection spectrum was used as a reference by measuring silicon carbide having a known reflectance. Measurement part is 1μ in diameter
m, a circular aperture of 14,000 cm, adjusted so that the aperture does not overlap the contour of the particles
^-1 (714 nm) to 28000 cm ^-1 (357 nm)
The transmission spectrum and the reflection spectrum were measured in the wave number range up to and the absorption spectrum was determined with 1-T (transmittance) -R (reflectance) as the absorption rate A. The absorption of silver halide was subtracted to obtain an absorbance A ', and the value obtained by integrating -Log (1-A') with respect to the wave number (cm ^-1 ) was set to 1/2 to obtain the light absorption intensity per unit surface area. . Integration range is 14000c
m ^-1 to 28000 cm ^-1 . At this time, a tungsten lamp was used as the light source, and the light source voltage was 8 V. In order to minimize damage to the dye due to light irradiation, a monochromator on the primary side was used, the wavelength interval was set to 2 nm, and the slit width was set to 2.5 nm. As for the absorption spectrum of the emulsion, the absorption spectrum of the dye alone was obtained by converting the infinite diffuse reflectance of the completed emulsion with respect to the emulsion without addition of the dye by the Kubelka-Munk method. The spectral sensitivity of the coated film was determined by exposure using a spectral exposure machine adjusted such that the number of photons of each wavelength was the same within the exposure wavelength range, and the exposure amount indicating a density of fog +0.2.

Further, a gelatin hardener and a coating aid were added to the obtained emulsion, and a gelatin protective layer was formed on a cellulose acetate film support so that the coated silver amount was 3.0 g-Ag / m ^2. At the same time. The resulting film was exposed to a tungsten bulb (color temperature 2854K) for 1 second through a continuous wedge color filter.
As a color filter, a wavelength range of 330 by combining a UVD33S filter and a V40 filter (manufactured by Toshiba Glass Co., Ltd.) for blue exposure to excite silver halide.
The sample was irradiated with light from 400 nm to 400 nm. In addition, a minus blue exposure for exciting the dye side is performed by passing through a Fuji Gelatin Filter SC-52 (manufactured by Fuji Film Co., Ltd.).
The light of 20 nm or less was blocked and the sample was irradiated. The exposed sample was developed at 20 ° C. for 10 minutes using the following surface developer MAA-1.

Surface developer MAA-1 Metol 2.5 g L-ascorbic acid 10 g Nabox (Fuji Film Co., Ltd.) 35 g Potassium bromide 1 g 1 liter with water pH 9.8 Developed film is Fuji Automatic Densitometer The optical density was measured by using the following formula.
The reciprocal of the amount of light required to give the optical density of is shown as a relative value based on Comparative Example 1. The results are shown in Tables 2 and 3. As shown in Table 2, by adding the two dyes of the present invention, multilayer adsorption can be performed on the particle surface, and the light absorption intensity per unit area of the particle surface (1/1 of the light absorption intensity of one particle). 2) has increased dramatically. Further, as shown in Table 3, the color sensitization sensitivity was significantly increased. Also, it is possible to increase the light absorption intensity in a narrow wavelength range,
It can be seen that high sensitivity can be obtained only for the target wavelength range.

[0111]

[Table 2]

[0112]

[Table 3]

[0113]

According to the present invention, a silver halide photographic material having high sensitivity is provided.

Claims (9)

[Claims] 2. The method according to claim 1, wherein the spectral absorption maximum wavelength is less than 500 nm and the light absorption intensity is 60 or more, or the spectral absorption maximum wavelength is 500.
In a silver halide photographic emulsion containing silver halide grains having a light absorption intensity of 100 nm or more, at least one of the sensitizing dyes used for spectrally sensitizing the emulsion has a charge in the molecule. A silver halide photographic emulsion characterized in that it is a dye that has no dye or forms an internal salt, has no charge as a whole, and has at least one aromatic ring in the molecule. 2. The silver halide photographic emulsion according to claim 1, wherein said sensitizing dye is a compound represented by the following general formula (I). General formula (I) In the general formula (I), Z1 and Z2 represent an atomic group necessary for forming a 5- or 6-membered nitrogen-containing heterocyclic ring. However, these may be condensed with a ring. R1 and R2 are alkyl groups,
Represents an aryl group or a heterocyclic group, and at least one of R1 and R2 is a group containing at least one aromatic ring. L1, L2, L3, L4, L5, L6, and L7 each represent a methine group. p1 and p2 represent 0 or 1. n1 represents 0, 1, 2, or 3. However, the dye represented by the general formula (I) has at least one anionic substituent required to form an inner salt, and has no charge as a whole molecule. 3. The silver halide photographic emulsion according to claim 1 or 2, wherein the maximum value of the spectral absorption by the sensitizing dye of the emulsion is Amax, the shortest wavelength indicating 80% of Amax and the shortest wavelength. The wavelength interval of long wavelength is 20 nm or more, and Am
3. The silver halide photographic emulsion according to claim 1, wherein a wavelength interval between the shortest wavelength and the longest wavelength which represents 50% of ax is 120 nm or less. 4. A silver halide photographic emulsion according to claim 1 or 2, wherein the maximum value of the spectral sensitivity of the emulsion by a sensitizing dye is Smax, the shortest wavelength and the longest wavelength representing 80% of Smax. The wavelength interval of the wavelength is 20 nm or more, and Smax
The wavelength interval between the shortest wavelength and the longest wavelength that represents 50% of the
3. The silver halide photographic emulsion according to claim 1, wherein the thickness is 20 nm or less. 5. The silver halide photograph according to claim 3, wherein the longest wavelength showing a spectral absorption of 50% of Amax is in the range of 460 nm to 510 nm, or 560 nm to 610 nm, or 640 nm to 730 nm. emulsion. 6. The silver halide photographic emulsion according to claim 4, wherein the longest wavelength exhibiting a spectral sensitivity of 50% of Smax is in the range of 460 nm to 510 nm, 560 nm to 610 nm, or 640 nm to 730 nm. 7. A silver halide photographic light-sensitive material containing at least one silver halide photographic emulsion layer, characterized in that it contains the silver halide photographic emulsion according to any one of claims 1 to 6. Silver halide photographic material. 8. The compound represented by the above general formula (I),
A compound represented by the general formula (I), wherein both R1 and R2 are groups containing at least one aromatic ring. 9. The compound according to claim 8, wherein at least one
A silver halide photographic light-sensitive material comprising: